Ultrafast Two‐Color X‐Ray Emission Spectroscopy Reveals Excited State Landscape in a Base Metal Dyad
Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light-induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H<sub>2</sub> production activity is studied using femtosecond X-ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time-dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the Fe<sup>II</sup> photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X-ray emission at the iron and cobalt K-edges in a two-color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.
Authors
- Christian Bressler (ORCID: https://orcid.org/0000-0001-9694-5495)
- Ahmet Kertmen
- Katharina Kubiček (ORCID: https://orcid.org/0000-0001-8481-2249)
- Aleksandr Kalinko (ORCID: https://orcid.org/0000-0002-0615-4735)
- Lennart Schmitz (ORCID: https://orcid.org/0009-0009-8760-1901)
- Dmitry Khakhulin (ORCID: https://orcid.org/0000-0002-4453-1204)
- Tae‐Kyu Choi (ORCID: https://orcid.org/0000-0002-3058-9165)
- Jacek Kubicki (ORCID: https://orcid.org/0000-0003-0790-5876)
- Peter Zalden (ORCID: https://orcid.org/0000-0002-8530-0576)
- Marina Huber‐Gedert
- Sophie E. Canton (ORCID: https://orcid.org/0000-0003-4337-8129)
- Matthias Bauer (ORCID: https://orcid.org/0000-0002-9294-6076)
- Angel Rodríguez-Fernández (ORCID: https://orcid.org/0000-0003-0587-5263)
- Natalia Piergies (ORCID: https://orcid.org/0000-0003-4899-3534)
- Thomas D. Kühne (ORCID: https://orcid.org/0000-0001-5471-2407)
- Mykola Biednov (ORCID: https://orcid.org/0000-0003-2219-155X)
- Frederico A. Lima (ORCID: https://orcid.org/0000-0001-8106-2892)
- Hossam Elgabarty (ORCID: https://orcid.org/0000-0002-4945-1481)
- Michał Nowakowski (ORCID: https://orcid.org/0000-0002-3734-7011)
- Wojciech Gawełda (ORCID: https://orcid.org/0000-0001-7824-9197)
- Mohammad Salem (ORCID: https://orcid.org/0000-0003-4159-0505)
- Natalia Lindner
Institutions
- Madrid Institute for Advanced Studies (ES)
- Universität Hamburg (DE)
- Paderborn University (DE)
- Helmholtz-Zentrum Dresden-Rossendorf (DE)
- Deutsches Elektronen-Synchrotron DESY (DE)
- Institute of Nuclear Physics, Polish Academy of Sciences (PL)
- Center for Advanced Systems Understanding (DE)
- Max Planck Institute for the Structure and Dynamics of Matter (DE)
- Hamburg Centre for Ultrafast Imaging
- Adam Mickiewicz University in Poznań (PL)
- Universidad Autónoma de Madrid (ES)
- Technische Universität Dresden (DE)
- European X-Ray Free-Electron Laser (DE)
- Technical University of Denmark (DK)
Publication Details
- Journal
- Advanced Science
- Published
- 2024-08-05
- DOI
- https://doi.org/10.1002/advs.202404348
- Citations
- 2
- Primary Topic
- X-ray Spectroscopy and Fluorescence Analysis
- Type
- article
- Field-Weighted Citation Impact
- 1.22
Funders
- Comunidad de Madrid
- Deutsche Forschungsgemeinschaft
- Bundesministerium für Bildung und Forschung
- Narodowe Centrum Nauki
- Universidad Autónoma de Madrid